Cationic thermosetting resin for improving wet strength of paper

ABSTRACT

Cationic thermosetting resins useful in imparting wet and dry strength to paper are prepared by reacting a heterocyclic dicarboxylic acid of the formula: WHERE R is alkylene or arylene with a diamine or polyalkylene polyamine, and itaconic acid to form a water-soluble polyamine polyamide polymer containing a plurality of spaced pyrrolidone groups, and then reacting said polymer with epichlorohydrin. An amino carbonyl compound may be included as a fourth reactant in forming the water-soluble polyamine polyamide polymer.   D R A W I N G

[ 1 Mar. 4, 1975 1 1 CATIONIC THERMOSETTING RESIN FOR IMPROVING WET STRENGTH OF PAPER [75] Inventors: Francis S. Munjat, Philadelphia;

,Samuel Ho Kim, Haverford, both of [73] Assignee: E.F. Houghton and Company,

Philadelphia, Pa.

[22] Filed: June 7, 1973 [21] Appl. No.1 367,802

[52] US. Cl 162/164, 260/78 SC, 260/78 A, 260/78 L, 260/78 TE [51] Int. Cl DZlh 3/58, C08g 20/20 [58] Field of Search 162/164, 168; 260/78 SC, 260/78 A, 78 L, 78 TF [56] I References Cited 0 UNITED STATES PATENTS 3.250,664 5/1966 Conte et ill. 162/164 3,320,215 5/1967 Conte et al. 162/168 3,395,130 7/1968 McDowell et a1. 162/164 3,640,841 2/1972 Winslow et a1. 162/164 3,761,350 9/1973 Munjat et a1. 162/164 OTHER PUBLICATIONS Morrison, R. T. and Boyd, R. N., Organic Chemistry, Sec. Ed, Allyn & Bacon, Inc., Boston, Mass, 1966, p. 1129.

Primary Examiner-S. Leon Bashore Assistant E.\'am1'nerWilliam F. Smith Attorney, Agent, or FirmHowson and Howson [57] ABSTRACT Cationic thermosetting resins useful in imparting wet and dry strength to paper are prepared by reacting a heterocyclic dicarboxylic acid of the formula:

O l HOOC- R- N CH CH COOH 10 Claims, N0 Drawings 3,869,343 r 1 v CATIONIC THERMOSETTING RESIN FOR IMPROVING WET STRENGTH OF PAPER' During the past two decades, a large number of dif- C ferent resins have been proposed for use in providing paper with improved wet strength. The greater portion R" (III) of such resins have been various types of polyamides rendered thermosetting by means of crosslinking agents such as halohydrins. An advantage of these resins resides in the fact that they are pH independent, and thus can be applied to paper stock under alkaline, neuwhere R is an alkylene radical containing from i to Hi tral or acid conditions. carbon atoms or an arylene radical and R" is an alkyl- An important property of any wet strength resin is ene radical containing from 3 to 10 carbon atoms:

the ability to provide paper with sufficient wet strength 0. from 1 to 3 mols of an amine which is a diamine offthe machine, i.e., simply dried as it emerges from of the formula:

the wet end of a typical Fourdrinier paper machine and l H N--R"NH lV rolled up. Aging at room temperature allows additional or a polyalkylene polyamine of the formula:

curing ofthe resin and provides increased wet strength. H n(R'NH),,H v,

Accelerated cure may be effected in systems which where R and R are alkylene groups containing from contain suitable drying sections. 2 to 6 carbon atoms, and n is'an integer from 1 to 5; and

Many of the various wet strength resins disclosed in the patent art provide inadequate off the machine wet d. from 1 to 2 mols 0f itaconic acid to form a water Strength, d i many instances i ffi i t wet soluble polyamine polyamide polymer, and then react- Strength after cum ing said polymer with epichlorohydrin to produce a Those resins which give adequate wet strength propthfinnosetting resinerties with economically feasible amounts of resin genh ater Soluble polyamine polyamide polymer has the following repeating structure:

crally do not provide adequate dry strength improve 1 is O to 4, and R, R, R", R', R" and n are as defined ment to the paper. This latter property is also of impor- 40 above. tance to the paper maker. a The pyrrolidone groups (asterisks) are generated by In accordance with this invention, there are provided providing an excess of itaconic acid to amine and holdnovel cationic thermosetting resins which provide ing the reaction temperature low to allow the addition paper with excellent wet strength, both off the machine to the double bond to take place followed by cyclizaand cured and also provide additional dry strength to tion. the-paper. in use these resins were found to produce i A preferred resin is obtained by reacting ldecreascd foaming in the paper machine and tissue of carboxypentyl-4-carboxypyrrolidine, caprolactam, diimproved softness. ethylene triamine, and itaconic acid to form thewater More particularly, the cationic thermosetting resins soluble polyamine polyamide polymer which is subseof this invention are prepared by reacting: quently rendered cross-linkahle by reaction with epi a. a hctcrocyclic (licarboxylie acid of the formula: chlorohydrin.

. Of particular importance in the novel improved wet strength resins of this invention is the presence of a r large number of spaced pyrrolidone groups, see forl mula VI above, for it is believed the improved proper- C CH2 ties of the resin, e.g. strength and toughness, are attributable to the presence of such groups.

The unsymmetrical heterocyclic dicarboxylic acid reactant (a) may be prepared by reacting itaconic acid CH COOH with an amino acid of formula (II) or a lactam of formula (III) in substantially equimollar proportions. The reaction may be carried out in aqueous solution; howwhere R is an alkylene radical containing from 1 to 10 ever, h amount f water d ShQuld b dj d t carbon atoms or an arylene adi a and for each mOl provide suitable reaction conditions to produce the of discarboxylic acid, product desired. Thus, although the aqueous solution b. frOm 0 0 4 111015 of an amino Carbonyl Compound of reactants may contain up to about 50% by weight of which is an amino ac d of h formulai water, subsequent concentration by distillation may re- 2 COOH duce the reaction solution to 5 to l0% of water. The reor a lactam of the formula: actants are merely mixed with water in the stated prodrolysis to amino acid. Initially, there is formed an intermediate tricarboxylic acid by addition of the itaconic acid methylene double bond to the amino group of the amino acid. The solution is then concentrated to form the heterocyclic dicarboxylic acid.

The reaction mechanism involved in forming one of the preferred heterocyclic dicarboxylic acids, namely l-(p-carboxyphenyl)-4Fcarboxypyrrolidone, may be illustrated by the following equations wherein itaconic acid and p-amino-benzoic acid are the reactants. The dicarboxylic acid separates from the reaction media and is isolated as a crystalline material.

1100 CNH2 HO CiJCHzCOOH 1120 no 0 cmicmjaco on H20 -rr20 HOOC N CHz- HCOOII (VII) polymer. However, in any particular polymer, the same or a different amino carbonyl compound may be used in forming the polymer as was employed in forming the heterocyclic acid.

As noted, the amino acids which may be used have the formula:

where R is an alkylene radical containing from 1 to carbon atoms or an arylene radical. The alkylene radical may be a straight or branched chain aliphatic group. Preferably, where R is an alkylene radical, the amino acids are alpha-substituted amino acids such as alanine, leucine, valine, and alpha-amino butyric acid. Other suitable amino acids include glycine, beta-alanine, 4- amino butyric acid. o-amino-caproic, acid, and l 1- amino undecanoic acid.

Aromatic amino acids which have been found useful in preparing the novel cationic thermosetting resins of the invention may contain such radicals as phenylene, naphthylene, etc., and alkyl substituted forms thereof. The amino groups may be directly substituted on the aromatic nucleus, or it may be on a terminal carbon atom of an alkyl group of l to 7 carbon atoms substituted on the aromatic ring. Similarly, the carboxylic acid group may be directly substituted on the aromatic ring or on a terminal carbon atom of an alkyl group containing from 1 to 7 carbon atoms substituted on the aromatic ring. Water solubility ofthe final resin characterizes the useful amino and carboxyl group containing compounds. Typical of useful aromatic amino carboxylicacids are 0, m, and p-amino benzoic acid, p-(2- amino-ethyl) benzoic acid and p-aminophenylacetic acid.

Lactams which are suitable for use in preparing the resins of this invention have the formula:

where R is an alkylene radical containing from 3 to 10 carbon atoms. Thus, useful lactams include pyrrolidone, e-caprolactam and the like, the latter lactam being particularly preferred.

In addition to the heterocyclic dicarboxylic acid and amino carbonyl compound, certain amines are also employed in combination therewith in preparing the water soluble polyamine polyamide polymers. As stated above, the amines may be certain alkylene diamines of formula (IV) or certain polyalkylene polyamines of formula (V).

In the diamines, the primary amine groups are separated by an alkylene radical containing from 2 to 6 carbon atoms. Thus, suitable diamines include ethylene, propylene, butylene, pentylene, and hexylene diamine. lithylene and propylene diamine are particularly preferred diamines inasmuch as they are somewhat more economical than the higher diamines.

v A variety'of polyalkylene polyamines including polyethylene polyamines, polypropylene polyamines, polybutylene polyamines, and the like can be employed to produce the polyamide, of which the polyethylenepolyamines represent an economically preferred class. More specifically, the polyalkylene polyamines employed are polyamines containing two primary amine groups, and at least one secondary amine group in which the nitrogen atoms are linked together by alkylene groups containing from 2 to 6 carbon atoms. The nitrogen atoms may be attached to adjacent carbon atoms in the ethylene groups or to carbon atoms futher apart, but not to the same carbon atom.

Polyamines such as diethylene triamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, and the like, which can be obtained in reasonably pure form can be used as well as mixtures thereof and mixtures of various crude polyamine materials. For example, the mixture of polyethylenepolyamines obtained by the reaction of ammonia and ethylencdichlorides, refined only to the extent of removal ofchlorides, water and excess ammonia, can be employed in the reaction with the dicarboxylic acid.

Most preferred are the polyethylene polyamines containing from two to four ethylene groups, two primary amine groups, and from one to three secondary amine groups.

The term polyalkylene polyamine employed in this specification and the claims, therefore, refers to and includes any of the polyalkylenepolyamines referred to above and to mixtures thereof.

6 Rather than using solely a diamine or a polyalkylene utes. During such heating, the components react to polyamine, mixtures of the two types of amines, e.g., a form short chain amide compounds of formula VIII, bemixt r of thyl n di mi a d di thyl t i i low, and water of condensation which is utilized in the may also be used. next step.

i i O C--CH ll 7 11 mm Nl-D CRN 0 0 (VIII) The remaining reactant is producing the water solu- In formula VIII, R, R, R, n and z are as set forth ble polyamine polyamide polymers is itaconic acid. above. This reactant functions to generate additional pyrrol- The intermediate reaction product (VIII) with added idone groups by reaction with amine groups at relawater is cooled, and an excess ofitaconic acid is added tively low reaction temperatures. with respect to carboxyl groups to amine, to obtain a The proportions of the reactants described above in further intermediate 0f the formula:

HO-C=O H0 O C CH O=C-0H 0 CH 2 HDC l'lH-CH -HN(R' NH) CRN o o cn 0 (1x) CH2 CH0 (NHRC) (HNR" )NHCH -CH-COH providing the improved resins is quite important. It was which is refluxed at a temperature .of from about 1 10 found that the mol ratios of reactants: (a) heteroc yclic to 140C, preferably from about 120C. to 136C, for dicarboxylic acid, (b) amino carbonyl compound, (c) 60 to 90 minutes to form the additional pyrrolidone diamine or polyalkylene polyamine, and (d) itaconic groups in the chain. In the case of larger polyalkylene acid employed in providing the water soluble polypolyamines where n equals 3 or more, the reaction amine polyamide polymer should be: product is added to the itaconic acid, and conversion (b) to (a) from about 0:1 to about 4;1 40 to the pyrrolidone acid ceases when the amine content (c) to (a) from about 1:1 to ab ut 3;] i is equivalent to the carboxylic acid content, but is only (d) to (a) from about 1:1 to about 2:1 about when n is equal to 4. This further intermedi- Preferred mol ratios of the four reactants in obtaining ate has the formula:

0 t (x) 0 CH2C\ o C-CHZ u0 N(R"'NH) can 0 o 0 --ca l n 1 1|- 2 aoc-ea-cn cn -cuc (NHRC) (NHR' n h) cu -CHCOH resins of optimum wet strength (uncured and after This intermediate product is then reacted with dicure) are (b) to (a) about 1:1, (c) to (a) about 3:1 and amine or polyamine to give a polyaminepolyamide (d) to (a) about 2:1. polymer which is water soluble. Condensation is ef- A preferred process by which the water soluble fected by raising the temperature to 185. Those mols polyaminepolyamide polymer may be prepared is by of water associated with the formation of the pyrrolheating a mixture of the heteroeyclic dicarboxylic acid idone ring are removed from the reaction site below (I) with the diamine (IV) or polyalkylene polyamine C. Water associated with polyamide formation is (V) in the presence or absence of the amino carbonyl removed above this temperature. The final polymer has compound II or III, at 150 to C. for 60 to 90 minthe formula:

1 water.

In order to render the water-soluble polyamine polyamide polymer crosslinkable or thermosetting, the polymer is reacted with epichlorohydrin. In carrying out this reaction, the polymer solution is first further diluted with water to provide a polymer solution containing from about 18 to 25% solids. While maintaining this solution at a temperature of from about 40 to about 60C., epichlorohydrin is added incrementally, e.g. dropwise. After addition of all the epichlorohydrin, the solution is heated to a temperature of from about 70 to 80C., until the pH of the system reaches 6.9 and/or a viscosity greater than I on the Gardner Holdt scale is obtained. The reaction mixture is then diluted and acidified with acid to give a final solution containing solids and having a pH of about 5. The Gardner Holdt viscosity is A to B;

Generally, from about 0.5 to about 1.8 mols of epichlorohydrin per secondary amine group should be used in rendering the polymer thermosetting; The preferred amount of epichlorohydrin used for such purpose is about one mol for each secondary amine group.

The cationic thermsetting resins of this invention impart improved wet and dry strength to paper (uncured or cured) whether made under acid, alkaline, or neutral conditions.

The resin preferably is incorporated into paper pulp at any point on the wet end of the paper machine, e.g., at the beater, stock chest, head box, etc. The resin may also be applied to a web of paper as by immersing the web in a solution of the resin, by spraying, etc., followed by heating to cure the resin. For most purposes, adequate wet strength is developed by simply drying the sheet and allowing natural aging to take place.

Adequate wet strength may be obtained by incorporating in the paper from about 0.15% to about 3% of the resin based on the dry weight of the pulp. Higher percentage additions may be made for special purposes.

Paper and pulp slurries having a pH of from 4.5 to l 1 may be effectively treated with resins of this invention.

The invention will be illustrated by means of the following examples:

EXAMPLE 1 Into a two liter flask equipped with condenser, ther- CH2-CHC(NHRC) (NHR N applied, and 108 g diethylenetriamine were added. The whole was then heated to 188C. with vacuum applied for one half hour at this temperature. The resin was di luted to solids content, and the Gardner Holdt viscosity was U at 25C. The amine equivalent of the polymer based on secondary amine is 272.3. 78 g of the above product were diluted with 1 16 m1 of water and heated to 50C. 16.5 g of epichlorohydrin were added dropwise, and the reaction was held at 70C. until the Gardner Holdt viscosity was greater than 1. It was then diluted with 343.5 ml of water of 10% solids and acidified to pH 5 with sulfuric acid. The ratio of epichlorophydrin to secondary amine was 1.25 to 1.

EXAMPLE 2 A polyamine polyamide polymer was prepared from 130 g of itaconic acid, 226 g of caprolactam, 36 ml of water, 206 g diethylenetriamine, 263 g of itaconic acid, and 108 g of diethylenetriamine using the procedure of Example 1 except that a three hour reflux period was utilized prior to the first amine addition. The viscosity of the polymer at 50% solids on the Gardner Holdt scale was U. A 10% solution was prepared for testing.

EXAMPLE 3 An 80% softwood and 20% hardwood bleached sulflte was beaten to a Canadian Freeness Value of 450 cc in a Valley beater. The pulp was adjusted to a pH value of 6.8 with sodium carbonate and variable amounts of the resin of Example 2 were applied to the stock (0 to 1%) based on the dry weight of pulp. 43 lb. per eam (TAPPI Standard) sheets were made on the Noble and Wood handsheet machine without a closed white water system. The handsheets were dried 3 minutes at C., and proportions of them were later cured for 1 hour at 105C.

Wet Strength oz/in Example 2 Resin Dried Cured Dry Strength oz/in Example 2 Resin Dried Cured The dry strengths show an improvement over the sample containing no resin.

at a temperature of from about 150 to mixture of:

What is claimed is: l. A cationic thermosetting resin prepared by heating about 165C. a

a. a heterocyclic dicarboxylic acid of the formula:

i JCHz where is an alkylene radical containing form 1 to 10 carbon atoms or an arylene radical, and for each mol of dicarboxylic acid,v

b. an amino carbonyl compound which is an amino acid of the formula H NR-COOH or a lactam of the formula:

where R is an alkylene radical containing from 1 to 10 carbon atoms or an arylene radical, and R is an alkylene radical containing from 3 to 10 carbon atoms;

c. a portion of the total amount of an amine which is a diamine of the formula H- NR"NH or a polyalkylene-polyamine of the formula H N-(- groups containing from 2 to 6 carbon atoms, and

n is an integer from 1 to cooling the resulting first intermediate reaction product 'Vlll, combining d. itaconic acid with said first intermediate reaction product in an amount so as to provide an excess of itaconic acid with respect to carbonyl groups to amine groups of said first intermediate and heating the mixture to a temperature of from about- 1 10 to about 140C. under reflux to obtain a second intermediate reaction product X, adding a further quantity of reactant (c) to said second intermediate reaction product and effecting condensation and re- 1 moval of water by heating the mixture to a temperature of about 185C, to form a water-soluble polyamide polyamine polumer XI, the proportions of reactants employed being from 0 to 4 mols of reactant (b), 1 to 3 mols of reactant (c) and 1 to 2 mols of reactant (d) for each mol of reactant (a), diluting said polyamine polyamide polymer with water to provide a solution containing from about 18 to about 25% by weight of polymer, adding to said polymer solution from about .05 to about 1.8 mols of epichlorohydrin per secondary amine 10 group in said polymer while maintaining the tem perature of said polymer solution at from about 40 to about C., and thereafter heating said polymer solution to a temperature of from about to about C. to provide a cationic thermosetting resin.

2. A cationic thermosetting resin according to claim 1 in which 1 mol of reactant (b), 3 mols of reactant (c) and 2 mols of reactant (d) for each mol of reactant (a) are used. and sufficient epichlorohydrin to convert all of the secondary amine groups of said polymer to tcr tiary amine groups is used.

3.A cationic thermosetting resin according to claim 2 in which the heterocyclic dicarboxylic acid reactant (a) is formed by reacting itaconic acid and an amino carbonyl compound which is caprolactam. 6- aminohexanoic acid, and'mixtures thereof.

4. A cationic thermosetting resin according to claim 3 in which reactant (a) is 1- carboxypentyl 4-carboxypyrrolidone, reactant (b) is caprolactam, and reactant (c) is diethylenetriamine.

5. A process for producing a water soluble polyamine polyamide polymer which comprises heating at a temperature from about to about C. a mixture of:

a. a heterocyclic dicarboxylic acid of the formula:

HOOC- R- N where R is an alkylene radical containing form 1 to 10 carbon atoms or an arylene radical, and R is an alkylene radical containing from 3 to 10 carbon atoms; and c. a portion of total amine which is a diamine of the formula H NR-NH or a polyalkyleneopolyamine of the formula H N-(R"-NH),,-H where R"and R" are alkylene groups containing from 2 to 6 carbon atoms, and n is an integer from I to 5; cooling the resulting first intermediate reaction product Vlll, combining d. itaconic acid with said first intermediate reaction product in an amount so as to provide an excess of itaconic acid with respect to carbonyl groups to amine groups of said first intermediate and heating the mixture to a temperature of from about 1 10 to about 140C. under reflux to obtain a second intermediate reaction product X, adding a further quantity of reactant (c) to said second intermediate reaction product and effecting condensation and removal of water by heating the mixture to a temper ature of about C, to obtain a water-soluble polyamine polyamide polymer Xl, the proportions of reactants employed being from to 4 mols of re-' actant (b), l to 3 mols of reactant (c) and 1 to 2 mols of reactant (d) for each mol of reactant (a), diluting said polyamine polyamide polymer with water to provide a solution containing from about 18 to about 25% by weight of polymer, adding to said polymer solution from about 0.5 to about 1.8 mols of epichlorohydrin per secondary amine group in said polymer while maintaining the temperature thereof at from about 40 to about 60C., and thereafter heating said solution to a temperature of from 70 to about 80C. to provide a cationic thermosetting resin.

6. The process according to claim in which 1 mol of reactant (b), 3 mols of reactant (c) and 2 mols of reactant (d) for each mol of reactant (a) are used.

7. The process according to claim 6 wherein 6- aminohexanoic acid and itaconic acid are first reacted to form as reactant (a) lcarboxypentyl- 4-carboxypyrrolidone, reactant (b) is caprolactam and reactant (c) is diethylenetriamine.

8. The process according to claim 7 in which said polyamine polyamide polymer is diluted with water to provide a soltion containing from about 18 to about 25% by weight of polymer. from about 0.5 to about 1.8 mols of epichlorohydrin per secondary amine group in said polymer are added to said polymer solution while the temperature thereof is maintained at from about 40 to about 60C.; and said solution is thereafter heated to a temperature of from to about "Cv to provide a cationic thermosetting resin.

9. An improved wet strength paper comprising a web of paper-making fibers and from about 0.15% to about 3.0% based on weight of dry fibers, of the cationic theremosetting resin of claim 1.

10. An improved wet strength paper comprising a web of paper-making fibers and from about 0.15% to about 3.0% based on weight of dry fibers of the cationic thermosetting resin of claim 4.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent: No. 3 9,3 3 Dated March 4, 1975 lnventofls) Francis S. Munj at and Samuel Ho Kim It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 5, line 16, "is" should read --in-- Column 8, line 29, "263" should read --273-- Column 9, line 59, "polumer" should read --polymer-- Column 9, line 66, ".05" should read --0.5--

Signed and Scaled this twen ty-eight D ay Of October 1 9 75 [SEAL] A ttest:

RUTH C. MASON C. MARSHALL DANN Arresting 0mm Commissioner ufParenls and Trademarks 

1. A CATIONIC THERMOSETTING RESIN PREPARED HYHEATING AT A TEMPERATURE OF FROM 150* TO ABOUT 165*C. A MIXTURE OF: A. A HETEROCYCLIC DICARBOXYLIC ACID OF THE FORMULA:
 2. A cationic thermosetting resin according to claim 1 in which 1 mol of reactant (b), 3 mols of reactant (c) and 2 mols of reactant (d) for each mol of reactant (a) are used, and sufficient epichlorohydrin to convert all of the secondary amine groups of said polymer to tertiary amine groups is used.
 3. A cationic thermosetting resin according to claim 2 in which the heterocyclic dicarboxylic acid reactant (a) is formed by reacting itaconic acid and an amino carbonyl compound which is caprolactam, 6-aminohexanoic acid, and mixtures thereof.
 4. A cationic thermosetting resin according to claim 3 in which reactant (a) is 1- carboxypentyl - 4-carboxypyrrolidone, reactant (b) is caprolactam, and reactant (c) is diethylenetriamine.
 5. A process for producing a water soluble polyamine polyamide polymer which comprises heating at a temperature from about 150* to about 165*C. a mixture of: a. a heterocyclic dicarboxylic acid of the formula:
 6. The process according to claim 5 in which 1 mol of reactant (b), 3 mols of reactant (c) and 2 mols of reactant (d) for each mol of reactant (a) are used.
 7. The process according to claim 6 wherein 6-aminohexanoic acid and itaconic acid are first reacted to form as reactant (a) 1-carboxypentyl- 4-carboxypyrrolidone, reactant (b) is caprolactam and reactant (c) is diethylenetriamine.
 8. The process according to claim 7 in which said polyamine polyamide polymer is diluted with water to provide a soltion containing from about 18 to about 25% by weight of polymer, from about 0.5 to about 1.8 mols of epichlorohydrin per secondary amine group in said polymer are added to said polymer solution while the temperature thereof is maintained at from about 40* to about 60*C., and said solution is thereafter heated to a temperature of from 70* to about 80*C. to provide a cationic thermosetting resin.
 9. An improved wet strength paper comprising a web of paper-making fibers and from about 0.15% to about 3.0% based on weight of dry fibers, of the cationic theremosetting resin of claim
 1. 10. An improved wet strength paper comprising a web of paper-making fibers and from about 0.15% to about 3.0% based on weight of dry fibers, of the cationic thermosetting resin of claim
 4. 